Acid dye composition for human hair



United States Patent O 3,352,755 ACID DYE COMPOSiTfON FOR HUMAN HAIRLouis L. Lerner, Chicago, and Helen E. Oberstar, Glen Ellyn, 111.,assignors to The Gillette Company, Boston, Mass, a corporation ofDelaware No Drawing. Filed Aug. 4, 1961, Ser. No. 129,251 2 Claims. (Cl.167-88) This invention relates to a dye composition suitable for dyeingkeratinous material such as human hair and pertains more specifically tosuch a dye composition containing acid dyes together with sufficientfree base to provide a pH from 8.5 to 12.5 in aqueous solution.

One object of the present invention is to provide a dye compositioneffective for dyeing keratinous material such as human hair, thecomposition being of such a nature that a mixture of two or more dyes inthe composition is absorbed selectively in predetermined ratio by thehair so that predictable and accurately reproducible results areobtained.

Another object is to provide such a dye composition containing acid dyescapable of dyeing human hair from an aqueous alkaline solution having apH from 8.5 to 12.5.

Still another object is to provide such a dye composition in which thedyes are medically safe, for example US. certified colors.

A further object is to provide a combined bleachingdyeing compositioneffective for dyeing human hair to a predictable and reproducible colorfrom an aqueous alkaline medium.

Other objects will be apparent from which follows.

While hair dye which is applied to the hair and not to any other part ofthe-body has no toxic 'etfect, it does occasionally come into contactwith the skin accidentally so that, in order to avoid problems ofpossible toxicity and/or sensitization, it isdesirable touse a medicallysafe dye such as a US. certified color rather than an uncertifiedcoal-tar dye. However, most of such medically safe dyes, for examplemost US. certified colors, are acid dyes; and it has not been possibleto obtain the desired range of colors from the certified colors whichare not acid dyes. In order to achieve lighter and more intense colorsthan are naturally present in. the hair, it is also desirable to bleachthe hair, preferably at the same time that the dyeing operation takesplace, using a'single combined bleaching-dyeing composition. Thebleaching agents of choice for use on human hair are peroxides, butthese materials areeifective as bleaching agents for hair only inaqueous alkaline solution, andit has generally been consideredimpossible to obtain effective dyeing from an alkaline medium using aciddyes.

It has now been discovered that by a suitable combination of ingredientsin addition to the acid dye itself, it is the description Patented Nov.14, 1967 "ice the salt, of a non-dyeing organic material having certainsolubility characteristics.

The dyes which are effective in the present invention are thoseconventionally known as acid dyes; that is, those organic dyes which dyeanimal fibers directly from an acidic dye bath. Included among thesedyes are most of the U5. certified colors, which are the dyes of choice.

The salts which may be employed in conjunction with the dye or mixtureof dyes include a wide variety of organic and inorganic salts which areinert to the dyes and other ingredients of the composition and which arenon-reactive with the hair. When organic salts are employed, they mustcontain no chains of carbon atoms exceeding six carbon atoms in length.Among such salts are those of monoand di-valent cations such as thealkali and alkaline earth metals, ammonia, lower alkaylamines containingfrom 1 to 4 carbon atoms, and mono-, diand tri-alkanolamines in whicheach alkanol group contains from 2 to 3 carbon atoms. The salts includethose having such anions as the chlorides, bromides, sulfates, acetates,borates, nitrates, citrates, lactates, bromates, chlorates, etc. Thesalts which are effective are those which are water-soluble; i.e., thosewhich are soluble to the extent of 0.1% by weight or more in water at 25C. The salt must be present in the composition in an amount at leastequal to the weight of the dye, the ratio of dye to salt being from 1:1to 1:20,000 by weight.

The third essential ingredient of the composition is a free base in anamount sufficient to produce a pH from 8.5 to 12.5 when the compositionis dissolved in water. When the dye composition is provided in the formof a dry solid material to be dissolved in an aqueous medium to form thedye bath, it is preferred that the free base be a solid material such assodium hydroxide, sodium carbonate, or 2-amino-2-methyl-l,3-propanediol.The dye composition may, however, be provided in the form of an possibleto obtain highly satisfactory hair dyeing from such compositions whenthey are employed in aqueous alkaline media. Moreover, it has been foundthat the dye compositions of the present invention offer the importantadvantage that the extent of absorption of dyes from a mixturecontaining a predetermined ratio of dyes is predictable and accuratelyreproducible for any given type of hair. M

The dye compositions of the present invention include, in addition tothe dye or mixture of dyes which includes acid dyes, a non-dyeing saltof a cation which is either monovalent or bivalent, and an alkalinematerial in an amount sufficient to provide a pH of 8.5 to 12.5 upondissolution of the composition in water. The compositions may alsoinclude, in a preferred embodiment, from 20% to 400%, based on the totalweight of the dye and aqueous solution, in which case it is alsopossible to employ such free bases as ammonium hydroxide,monoethanolamine, and the like. i

While dye compositions containing the dye, salt, and free base asdescribed above are effective for the purpose of the present inventionwhen applied to the hair in the form of an aqueous solution, optimumresults are obtained by adding to the composition from 20% to 200%,based on the total weight of dye and salt, of a non-dyeing organicmaterial having certain solubility characteristics as hereinafterdefined. Up to 400% by Weight of this material, based on the weight ofdye and salt, may be added if desired. The organic material may beeither liquid or solid at ordinary temperatures, but must not becompletely miscible at ordinary temperatures with the aqueous dye, salt,free base com-positions described above. It. may be substantiallycompletely immiscible with or substantially insoluble in suchcompositions, or it may be miscible with them only to a limited extent.In any event, it must possess a water solubility so limited that whenmixed with an aqueous salt solution in the ratio of 4 parts of theorganic material to 10 parts of water to 1.4 parts salt by weight at 25C., it forms a separate phase and does not completely dissolve in or mixwith I aqueous phase. In addition, the organic material must have asolvent power for the dye or mixture of dyes in the dye compositionwhich is approximately equal to the solvent power of water. This solventpower can be determined by dissolving the dye compositionincluding thedye or dye mixture, the salt, and the free base in aquewhen the dyeconcentration in the aqueous phase at the beginning of the test is quitelow; a dye concentration of 0.0005 by weight in the aqueous phase hasproved to be very satisfactory. If under these conditions visual.

inspection of the two layers show that the organic material phase hasextracted a portion only of the dye from the aqueous phase, then theorganic material is satisfactory for the purpose of the presentinvention. On the other hand, if the organic phase has extracted none ofthe dye from the aqueous phase or if it has extracted substantially allof the dye from the aqueous phase, the organic material is notsatisfactory for the purpose of the present invention.

Among organic materials which have been found satisfactory for purposesof the present invention are such organic alcohols as n-butyl alcohol,n-amyl alcohol, noctyl alcohol, benzyl alcohol, terephthalyl alcohol,phenyl ethyl alcohol, and the like, cyclohexanone, tetrahydrofuran,aniline, chlorobenzene, camphor, Xylene, toluene, and various othermaterials. For most purposes the alcohols are preferred, benzyl alcoholbeing the material of choice. The amount of organic material may varyfrom to 400%, based on the total weight of the dye and the salt.

As indicated above, the dye composition may be provided in dry solidform to be dissolved in an aqueous medium to form the dye bath, in whichcase each of the ingredients is itself preferably solid. The dyecomposition may also conveniently be supplied to the consumer. in theform of a paste, cream, or free-flowing aqueous liquids. It is alsopossible to employ hair-bleaching agents in combination with theremaining ingredients in the present invention to provide combinedbleaching-dyeing compositions. When the dye composition including freebase is provided in dry solid form, the bleaching agent, in solid form,may be stored in admixture with the remaincler of the composition. Whenthe dye composition is provided in the form of paste, cream or solution,however, the bleaching agent, whether solid or not, must be keptseparate from the remainder of the composition until shortly before use.

Bleaching agents which may be used effectively in combinedbleaching-dyeing compositions include urea peroxide and sodium carbonateperoxide, both of which may be added to the composition in dry solidform, and hydrogen peroxide which may be employed in the form of apaste, cream or free-flowing aqueous solution. When the bleaching agentis hydrogen peroxide, it must be supplied in an aqueous medium, it mustbe packaged separately from the dye or mixture of dyes, and it must bemaintained at an acidic pH. Consequently, the free base must under theseconditions be packaged separately from the bleaching agent, beingpackaged either by itself or in admixture with the dye composition. Theamount of free base should be such, as is readily determined by thoseskilled in the art, as to provide a pH from 8.5 to 12.5 in the aqueousdye bath in the form in which it is applied to the hair.

The water content of the compositions may vary over a wide range. Itwill be understood that is some cases it may be desirable to supply thedye composition in the form of a highly concentrated aqueous solutionadapted to be diluted with additional water by the ultimate consumerimmediately prior to use. The water content of the aqueous compositionin the form in which it is actually applied to the hair for dyeingpurposes may also vary over a considerable range, depending upon theintensity of color desired and the length of time available formaintaining the dye bath in contact with the hair, aswell'as upon thetemperature at which the dyeing operation is carried out. In general,the water content of the dye bath in the form in which it is applied tothe hair will range from 65% to 90% by weight,

solution, in which case one or more ingredients may be Such optionalingredients as are commonly employed in conventional hair dye and hairbleach compositions may also be employed in the compositions of thepresent invention. Among such additives are perfumes, opacifiers, andthickeners, e.g., ethoxylated fatty alcohols, carboxylated vinylpolymers, ethoxylated tallow alcohols, stabilizers, etc. However, it isessential that the composition contain no reducing agents which reactwith the hair both because they might tend to damage the hair andbecause they are incompatible with the oxidizing bleaching agents.

The following specific examples. are intended to illustrate more clearlythe nature of the invention without placing any restriction upon itsscope.

Example 1 The following composition was prepared, in which the parts areby weight:

- Parts D & C Brown No. 1 (01. No. 20170) 0.5 Benzyl alcohol 3.8 Sodiumsulfate 4.0 Ammonium hydroxide (28 B.) 4.0 Water, to make 100.0

The composition was applied to white hair by means of a sponge andallowed to stand for 15 minutes at 26 C., after which the hair wasrinsed in water, shampooed This composition was applied to hair asdescribed in Example 1, the. result being a red coloration.

Example 3 The following composition was prepared, in which the parts areby weight:

Parts D & C Brown No. 1 (Cl. No. 20170) 0.5 Benzyl alcohol 3.8 Lithiumbromide 4.0 Ammonium hydroxide (28 B.) 4.0 Water, to make 100.0

The composition was employed to dye white hairusing the proceduredescribed in Example 1; the finished hair was found to exhibit a lightbrown color.

Example 4 The following composition was prepared, in which the parts areby weight:

Parts D & C Brown No. 1 (0.1. No. 20170) 0.5 N-amyl alcohol 3.0 Sodiumsulfate 4.0 Ammonium hydroxide (28 B.) 4.0 Water, to make 100.0

The composition was employed to dye white hair by the procedure ofExample 1; the finished hair was found to exhibit a light brown colorsimilarto that produced in Example 3 above.

Example 5 The following compositions were prepared, in which the partsare by weight:

N-butanol 20.0

Each dye composition containing the particular nondyeing organicmaterial in the quantity specified was employed to dye white hair by theprocedure of Example 1 above. In each case the dye composition washighly effective in producing a distinct and intence color in the whitehair.

Example 6 The following compositions were prepared, in which the partsare by weight:

. Parts D & C Brown No. 1 (Cl. No. 20170) 0.5 Benzyl alcohol 3.8Ammonium hydroxide (28 B.) 4.0 Non-dyeing salt, as specified in thefollowing table. Water, to make 100.0

Non-dyeing salt: v

Sodium sulfate 2.0 Sodium sulfate 6.0

Sodium sulfate a 15.0 Magnesium sulfate- 2.0- Magnesium sulfate 10.0Ammonium chloride 2.0 Ammonium chloride 10.0

Sodium sulfite 2.0 Sodium sulfite 10.0 Sodium bromate 2.0 Sodium bromate10.0

I Exam-pl 7 i 'The following compositions. were prepared, in which theparts are by weight:

Parts Ext. D &.C Violet No. 2 (Cl. No. 60730) 0.5 Benzyl alcohol 3.8Ammonium hydroxide (28 B.) 4.0 Non-dyeing salt, as shown in thefollowing table. Water, to make '100.0

Non-dyeing salt:

Sodium sulfate 2.0

- Sodium sulfate 6.0

Sodium sulfate 15.0 Ammonium chloride 2.0 Ammonium chloride 10.0 Sodiumsulfite 2.0 Sodium sulfite 10.0 Sodium bromate 2.0 Sodium bromate, 10.0

In each case when employed in the procedure described in Example 1above, the dye compositions produced very marked and intense colorationsin white hair.

Example 8 The following compositions were prepared, in which the partsare by weight:

- Parts D & C Brown No. 1 (Cl. No. 20170): 0.5 Benzyl alcohol 3.8 Sodiumsulfate 5.0 Free base, as shown in the following table. Water, to make100.0

Free base:

Ammonium hydroxide (28 B.) 1.0 Ammonium hydroxide (28 B.) 2.0 Ammoniumhydroxide (28 B.) 4.0 Ammonium hydroxide (28 B.) 6.0 Monoethanolamine1.0 Monoethanolamine 4.0 Sodium hydroxide 1.0

In the case of each of Examples 1 to 8, the procedure described inExample 1 above produced the desired intense coloration in the hair. Thecomposition containing sodium hydroxide produced a stronger colorationthan did the others and exhibited a higher pH, about 12.0-12.1, than didthe compositions containing the other free bases, which had a pH ofabout 11.7 (ammonium hydroxide) and 11.2 (monoethanolamine),respectively.

Similar results were obtained when the 3.8 parts of benzyl alcohol inthe foregoing compositions were replaced by 1.0 part of N-hexane.

Example 9 The following composition was prepared, in which the parts areby weight:

Parts D & C Black No. 1 (C.I. No. 20470) 0.0133 Ext. D & C Red No. 13(Cl. No. 27290) 0.0033 Thickener comprising high molecular weightcarboxylated vinyl polymer (Carbopol 934) 2.0 Ammonium hydroxide (28 B.)5.0 Benzyl alcohol 3.8 Sodium sulfate, anhydrous 4.0 Water 85.0

The composition was applied to white .hair with a polyurethane spongeover a period of 2% to 3 /2 minutes, then left on the hair for 5 to 6minutes at roomtemperature, after which the head was rinsed with water,given two sudsings with a commercial shampoo, and again rinsed withwater. The finished hair had a pale, attractive, blue-gray color whichexhibited very satisfactory permanency over a three to four week period,during which the hair was frequently shampooed.

Example 10 I The following composition was prepared, in which the partsare by weight:

The creamy composition which resulted from this preparation was appliedto a head of hair which has a fading, graying, light brownish-red colorby means of a polyurethane sponge over a period of 5 minutes and allowedto remain on the air for an additional 5 minutes at 7. room temperature,after which the head was rinsed with water, given two sudsings with acommercial shampoo, and again rinsed with water. The result was anattractive titian color which exhibited satisfactory permanency over afour-to six-week period with frequent shampooing.

Exam ple 1 1 The following composition was prepared, in which the partsare by weight:

Parts D & C Brown No. 1 (Cl. No. 20170) 0.8 Ext. D & C Violet No. 2 (Cl.No. 60730) 0.2

Thickener comprising high molecular weight carboxylated vinyl polymer(Carbopol 934) 2.0 Benzyl alcohol 8.0 Ammonium hydroxide (28 B.) 8.0Sodium sulfate, anhydrous 8.0

Water 73.0

This composition was mixed in equal volumes with an aqueous solutioncontaining 6%by weight of hydrogen peroxide. The mixture was applied tomedium brown colored hair and allowed to remain in contact with the hairfor 15 minutes at room temperature,,after which the hair was rinsed withwater, sudsed twice with a commercial shampoo, then rinsed again. Thefinished hair possessed a .drab light brown color.

Example 12 The following composition was prepared, in which the partsare by weight:

Parts D & C Black No. 1 (Q1. No. 20470) 0.5 Benzyl alcohol 2.0 Ammoniumhydroxide (28 B.) 4.0 Sodium sulfate 4.0

Water, to make 100.0

The composition was applied to hair and allowed to remain for 15 minutesat room temperature, after which the hair was rinsed with water, sudsedtwice with a commercial shampoo, then rinsed again with water. Theresult was a blue-green color in the hair.

Similar results were obtained when there were added to the foregoingcomposition 1.8 parts of N-butanol and again when there were added tothe composition 1.8 parts of mineral oil instead of butanol.

Example 13 The following composition was prepared, in which the partsare by weight:

Parts Ext. D & C Violet No. 2 (0.1. No. 60730) 1.0 Benzyl alcohol 7.6Sodium sulfate, anhydrous 8.0 Thickener 2.0 Ammonium hydroxide (28 B.)8.4 Water, to make 100.0

The following composition was prepared, in which the parts are byweight:

Parts D & C Brown No. 1 (Cl. No. 20170) 0.41 Ext. D & C Violet No. 2(Cl. No. 60730) 0.60

Parts Ext. D & C Red. No. 13 (0.1. No. 27290) a--- 0.50 Benzyl alcohol8.00 Sodium sulfate, anhydrous 8.00

Thickener comprising high molecular weight carboxylated vinyl polymer(Carbopol 934) 2.00 Ammonium hydroxide (28 B.) 2.48

Water, to make 100.00

This composition, having a pH of approximately 8.7, was applied to hairand allowed to remain for fifteen minutes at room temperature, afterwhich the'hair was rinsed with water, sudsed twice with a commercialshampoo, then rinsed again with water. The result was a titian shade inthe hair.

Example 15 The following composition was prepared, in which the partsare by weight:

Parts D & C Brown No. 1 (CI. No. 20170) 0.82 Ext. D & C Violet No. 2(Cl. 60730) 0.09 Ext. D & C Red No. 13 (C.I.,No. 27290) 0.09 Benzylalcohol 8.00 Sodium sulfate, anhydrous 8.00 Thickener comprising highmolecular weight carboxylated vinyl polymer (Carbopol 934) 2.00 Ammoniumhydroxide (28 B.) 3.58 Water, to make 100.00

This composition, having a pH of about 9.4, was mixed with an equalvolume of a creamy peroxide bleach composition as described in Example13 above. The mixture was applied to medium brown hair in the mannerdescribed in Example 13 above, whereupon the hair was found to have atitian shade.

Example 16 The following composition was prepared, in which the partsare by weight:

Parts D & C Black No. 1 (Cl. No. 20470) 0.25 Ext. D & C Red No. 13 (Cl.No. 27290). 0.25 Benzyl alcohol 8.00 Sodium sulfate, anhydrous 8.00Thickener comprising high molecular weight carboxylated vinyl. polymer(Carbopol 934) 2.00 Ammonium hydroxide (28 B.) 2.58

Water, to make 100.00

This composition, havinga pH of about 8.9, was applied to white hair asdescribed in Example 14, producing a soft blue-gray color.

Example 17 The following composition was prepared, in which the partsare by weight:

Parts D & C Brown No. 1 (Cl. No. 20170) 0.40 Ext. D & C Violet No. 2(Cl. No. 60730) 0.10 Benzyl alcohol 8.00 Sodium sulfate, anhydrous 8.00Thickener comprising high molecular weight car boxylated vinyl polymer(Carbopol 934) 2.00 Ammonium hydroxide (28 B.) 2.58 Water, to make100.00

This composition, having a pH of about 8.6, was ap-.

plied to gray hair as described in Example, 14 above and was found toproduce a brown shade.

Example 18 e The following composition was prepared, in which the partsare by weight:

Parts D & C Brown No. 1 (Cl. No. 20170) 1.0 Benzyl alcohol 8.0 Sodiumsulfate, anhydrous 8.0 Ammonium hydroxide (28 B.) 8.0 Cornstarch 50.0

The mixture was a moist freedlowing powder which could readily bepackaged in a metal or plastic foil envelope and which resulted in asolution having a pH of about 10.2 when dissolved in water. It was mixedimmediately prior to use with 67 parts by weight of a 3% aqueoushydrogen peroxide solution.

The resulting mixed solution was applied to gray hair by the proceduredescribed in Example 14 and was found to produce a brown shade.

Example 19 The following composition was prepared in which the parts areby weight:

Parts D & C Brown NO. 1 (Cl. No. 20170) 1.0 Benzyl alcohol 8.0 Sodiumsulfate, anhydrous 8.0 Ammonium hydroxide (28 B) 8.0 White dextrin 45.0

Example 20 The following composition was prepared, in which the partsare by weight:

Parts D & C Brown No. 1 (Cl. No. 20170) 0.5 Benzyl alcohol 4.0 Sodiumsulfate, anhydrous 4.0 Sodium carbonate peroxide 12.0 White dextrin 20.0

The resulting composition was a completely dry powdered material whichcould readily be packaged in the same fashion as the powders of Examples18 and 19 above and which produced when dissolved in 100 parts by Weightof water an aqueous solution having a pH of about 9.5. The solution,when applied to gray or white hair by the procedure described in Example12, above produced a brown shade.

Example 21 The following composition was prepared, in which the partsare by weight:

Parts Ext. D & C Violet N0. 2 (Cl. No. 60730) 0.30 D 8: C Green N0. (Cl.No. 61570) 0.03 Sodium sulfate, anhydrous 10.00 Ammonium hydroxide (28B.) 6.90 Water, to make 100.00

The solution having the foregoing composition and a pH of about 10.4 wasmixed immediately prior to use with an equal volume of a creamy peroxidebleach composition as described in Example 13 above. The mixed solutionsupon application to gray hair as described in Example 13 produced a paleblue shade.

Example 22 The following composition was prepared, in which the partsare by weight:

Parts D & C Brown No. 1 (Cl. No. 20170) 0.32 Ext. D & C Orange No. 3(CI. No. 14600) 0.35 D & C Black No. 1 (Cl. No. 20470) 0.15 Sodiumsulfate, anhydrous 10.00 Ammonium hydroxide (28 B.) 5.80 Water, to make100.00

The solution, having a pH of about 9.3, was applied to hair by theprocedure described in Example 12 above, producing an auburn shade.

Example 23 The following composition was prepared, in which the partsare by weight:

Parts Ext. D & C Orange No. 3 (Cl. No. 14600) 0.5 D & C Black No. 1 (CI.20470) 0.5 Sodium sulfate, anhydrous 10.0 Ammonium hydroxide (28 B.) 6.9Water, to make 100.0

The solution, having a pH of about 10.1, was mixed with a creamyperoxide and applied to hair as described in Example 13, except that thehead of the individual was wrapped in a turban during the 15-minuteperiod so as to provide a temperature somewhat greater than roomtemperature. The hair displayed a warm brown shade.

Any of the conventional methods of application of dye compositions tohair may be employed in using the compositions of the present invention.In the case of liquid compositions, they may be poured repeatedlythrough the hair until a satisfactory level of color has been attainedor they may be applied to the hair by a variety of daubers until thehair is thoroughly wetted and allowed to remain until the desired depthof color is achieved. If the composition is a cream or paste, it may beapplied to part or all of the head of hair as desired and allowed toremain until the requisite depth of color has been attained. Theprocedure may be carried out either at ordinary room temperature withthe head exposed to the atmosphere; or elevated temperatures may beemployed by means of electrically heated caps, hot towels over plasticcaps, or other sources of heat.

Although specific embodiments of the invention have been describedherein, it is not intended to limit the invention solely thereto, but toinclude all of the obvious variations and modifications within thespirit and scope of the appended claims.

What is claimed is:

1. A hair dye composition consisting essentially of an acid dye, a watersoluble salt selected from the class consisting of the chlorides,bromides, sulfates, acetates, borates, nitrates, citrates, lactates,bromates and chlorates of alkali metals, alkaline earth metals, ammonia,lower alkylamines containing from 1 to 4 carbon atoms, and mono-, di-,and tri-alkanolamines in which each alkanol group contains from 2 to 3carbon atoms, said salt being chemically inert to the hair and to theremaining ingredients of the composition, the ratio of dye to salt beingfrom 1:1 to 1120000 by weight, and a free base in an amount sufiicientto produce a pH of 8.5 to 12.5 in an aqueous solution containing thecomposition.

2. A hair dye composition consisting essentially of an acid dye, a watersoluble salt selected from the class consisting of the chlorides,bromides, sulfates, acetates, borates, nitrates, citrates, lactates,bromates and chlorates of alkali metals, alkaline earth metals, ammonia,lower alkylamines containing from 1 to 4 carbon atoms, and mono-, di-,and tri-alkanolamines in which each alkanol group contains from 2 to 3carbon atoms, said salt being chemically inert to the hair and to theremaining ingredients of the composition, the ratio of dye to salt beingfrom 1:1 to 1:20000 by weight, and a free base in an amount sufficientto produce a pH of 8.5 to 12.5 in an aqueous solution containing thecomposition, said free base being selected from the class consisting ofsodium hydroxide, sodium carbonate, 2-amino-2-methyl-1,3- propanediol,ammonium hydroxide, and monoethanolamine, said composition containing inaddition from 20% -to 400%, based on the total weight of said dye andsaid benzyl alcohol, terephthalyl alcohol, phenyl ethylalcohol,cyclohexanone, tetrahydrofuran, aniline, chlorobenzene, camphor, xyleneand toluene, said organic material being one which forms a separatephase when mixed with Water in the ratio 4 parts by weight of organicmaterial to 10 parts of Water at 25 C., and which, in contact with aseparate aqueous phase containing said dye, said salt, and said freebase, extracts a portion only of said dye therefrom in three hours at 25C.

References Cited UNIT-ED STATES PATENTS 2,283,350 5/1942 :Baum -1, 1678.8.1 2,643,211 6/1953 Den Beste 16788 2,776,668 1/1957 Morgan 167-88X15 12 OTHER REFERENCES Colour Index, 2nd edition, The AmericanAssociation of Textile Chemists and Colorists, Lowell, Mass, 1956, vol.I, pp. 1001-2, 1062, 1064, 1123, 1211, 1318 and 1375.

Goldemberg: Journal of Society of Cosmetic Chemists, 10, pp. 291306,1959, (pp. 300-301 relied on).

Merck Index, seventh edition, .Merck and C0 Inc., New Jersey, 1960, (pp.535 and 962 relied on).

ALBERT T. MEYERS, Primaly Examiner.

M. O. WOLK, F. CACCIAPAG LIA, J; LEVITT,

Examiners. V. CLARKE, Assistant Examiner.

1. A HAIR DYE COMPOSITION CONSISTING ESSENTIALLY OF AN ACID DYE, A WATERSOLUBLE SALT SELECTED FROM THE CLASS CONSISTING OF THE CHLORIDES,BROMIDES, SULFATES, ACETATES, BORATES, NITRATES, CITRATES, LACTATES,BROMATES, AND CHLORATES OF ALKALI METALS, ALKALINE EARTH METALS,AMMONIA, LOWER ALKYLAMINES CONTAINING FROM 1 TO 4 CARBON ATOMS, ANDMONO-, DI-, AND TRI-ALKANOLAMINES IN WHICH EACH ALKANOL GROUP CONTAINSFROM 2 TO 3 CARBON ATOMS, SAID SALT BEING CHEMICALLY INERT TO THE HAIRAND TO THE REMAINING INGREDIENTS OF THE COMPOSITION, THE RATIO OF DYE TOSALT BEING FROM 1:1 TO 1:2000 BY WEIGHT, AND A FREE BASE IN AN AMOUNTSUFFICIENT TO PRODUCE A PH OF 8.5 TO 12.5 IN AN AQUEOUS SOLUTIONCONTAINING THE COMPOSITION.